CN116041936A - Resin composition, prepreg and application thereof - Google Patents

Abstract

This application provides a resin composition, which can solve the problem of polyphenylene ether resin by combining modified polyphenylene ether resin, hydrocarbon resin and bismaleimide resin, and synergizing with flame retardants, crosslinking agents and initiators. The problem of its own rigid structure reduces the coefficient of thermal expansion of the resin composition, thereby solving the problem of warpage expansion. And the reasonable compatibility of modified polyphenylene ether resin, hydrocarbon resin, bismaleimide resin and crosslinking agent types and components can ensure low thermal expansion coefficient, low dielectric constant and low dielectric loss of the resin composition . At the same time, the resin composition of the present application can improve the solubility of the bismaleimide resin under the synergistic effect of each component, and can enhance the compatibility of each component.

Description

Resin composition, prepreg and application thereof

Technical Field

The present invention relates to the field of polymer materials, and specifically relates to a resin composition, a prepreg and applications thereof.

Background Art

In recent years, with the development of electronic information technology, the miniaturization and high density of electronic equipment installation, the large capacity and high speed of information, higher requirements have been put forward for the performance of electronic materials. This has put forward higher requirements for the performance of substrate materials carrying semiconductor components, especially for the coefficient of thermal expansion (CTE).

In the semiconductor packaging process, if the difference in thermal expansion coefficient between the semiconductor element and the substrate material is too large, stress is easily generated to cause material warping, resulting in serious problems such as poor connection between the semiconductor element and the substrate material, and between the substrate material and the PCB. Therefore, for the substrate material, a lower thermal expansion coefficient is required in the X/Y axis direction. At the same time, with the development and scale of 5G, the high speed and high frequency of transmission signals require materials to have better dielectric properties, that is, lower dielectric constant and dielectric loss.

Summary of the invention

In view of the above problems existing in the prior art, the purpose of the present application is to provide a resin composition, a prepreg and its application. The resin composition has a lower thermal expansion coefficient, and also has a lower dielectric constant and dielectric loss.

To achieve the above objectives, this application adopts the following technical solutions:

The present application provides a resin composition, which comprises the following components in parts by weight:

Wherein, the structural formula of the modified polyphenylene ether resin is:

Wherein, m and n are both positive integers, the sum of m and n is 5 to 50, the number average molecular weight of the modified polyphenylene ether resin is 500 to 4000; and R is a cycloalkyl group or an asymmetric branched alkyl group.

In one embodiment, the cycloalkyl group is a C ₅ -C ₇ cycloalkyl group;

The asymmetric branched alkyl group is a C ₃ -C ₆ asymmetric branched alkyl group.

In one embodiment, the ratio of the modified polyphenylene ether resin to the hydrocarbon resin is 100 parts: (20-60) parts by weight.

In parts by weight, it includes the following components:

In one embodiment, the cycloalkyl group is selected from any one of cyclopentyl, cyclohexyl, cycloheptyl, 3-methylcyclohexyl, 3-methylcycloheptyl or 3,5-dimethylcyclohexyl;

The asymmetric branched alkyl group is selected from any one of methylethyl, methylpropyl, ethylpropyl, methylbutyl or ethylbutyl.

In one embodiment, the hydrocarbon resin includes one or two of polybutadiene and a copolymer of butadiene and styrene.

In one embodiment, the hydrocarbon resin is a copolymer of butadiene and styrene.

Furthermore, the number average molecular weight of the copolymer of butadiene and styrene is 1000-20000, the molar content of butadiene in the copolymer of butadiene and styrene is 40%-90%, and the molar content of styrene in the copolymer of butadiene and styrene is 10%-60%.

In one embodiment, the resin composition has one or more of the following characteristics:

(1) The bismaleimide resin includes one or more of biphenyl bismaleimide resin, polyphenylmethane maleimide and bis(3-ethyl-5-methyl-4-maleimidophenyl)methane;

(2) the crosslinking agent includes one or more of allyl compounds, styrene, divinylbenzene, acrylate compounds, methacrylate compounds, polybutadiene and bismaleimide compounds;

中的一种或多种，其中，n1、n2均为正整数；(3) The flame retardant includes

One or more of, wherein n1 and n2 are both positive integers;

(4) The initiator includes one or more of α,α′-bis(tert-butylperoxym-isopropyl)benzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, benzoyl peroxide, 3,3′,5,5′-tetramethyl-1,4-diphenolquinone, tetrachlorobenzoquinone, 2,4,6-tri-tert-butylphenoxy, tert-butylperoxyisopropylmonocarbonate and azobisisobutyronitrile;

(4) The inorganic filler includes one or more of silicon dioxide, aluminum oxide, titanium oxide, mica, aluminum hydroxide, magnesium hydroxide, talc, aluminum borate, barium sulfate and calcium carbonate.

。In one embodiment, the flame retardant is

.

The present application also provides a prepreg, which comprises a substrate and the resin composition described in any one of the above embodiments loaded on the substrate.

The present application also provides a use of the prepreg described in the above embodiment in the preparation of a laminate, a copper-clad laminate or a wiring board.

The present application provides a kind of resin combination, by modified polyphenylene ether resin, hydrocarbon resin and bismaleimide resin are matched, and coordinated with flame retardant, cross-linking agent and initiator, it is possible to solve the problem of rigid structure of polyphenylene ether resin itself, reduce the thermal expansion coefficient of the resin combination, and then can solve its warping expansion problem. And the reasonable compatibility of modified polyphenylene ether resin, hydrocarbon resin, bismaleimide resin and cross-linking agent type and component can ensure the low thermal expansion coefficient, low dielectric constant and low dielectric loss of resin combination. Meanwhile, the resin combination of the present application can improve the solubility of bismaleimide resin under the synergistic effect of each component, and can enhance the compatibility of each component.

DETAILED DESCRIPTION

The following is a further detailed description of the resin combination, prepreg and application of the present application in conjunction with specific embodiments. The application can be realized in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the application more thorough and comprehensive. Of course, they are merely examples, and purpose is not intended to limit the application.

When a numerical range is disclosed herein, the above range is considered to be continuous and includes the minimum and maximum values of the range, as well as every value between such minimum and maximum values. Further, when a range refers to an integer, every integer between the minimum and maximum values of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be combined. In other words, unless otherwise indicated, all ranges disclosed herein should be understood to include any and all subranges included therein.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application belongs. The terms used herein in the specification of this application are only for the purpose of describing specific embodiments and are not intended to limit this application. Unless otherwise specified or there is a contradiction, the terms or phrases used herein have the following meanings:

In the present application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

In the present application, the percentage content, unless otherwise specified, refers to mass percentage for solid-liquid mixing and solid-solid mixing, and volume percentage for liquid-liquid mixing.

In this application, when it comes to percentage concentration, unless otherwise specified, it refers to the final concentration. The final concentration refers to the proportion of the added component in the system after the addition of the component.

In the present application, "*" indicates a connection site.

In the present application, when a linking site is not specified in a group, it means that an optional linking site in the group can be used as a linking site.

中R与苯环的任一可取代位点相连，且R的官能团不限于1个。例如，

指苯环上含有1～6个R官能团。合适的实例包括但不限于：

In the present application, the single bond to which the substituent is connected runs through the corresponding ring, indicating that the substituent can be connected to any position of the ring, for example

In the formula, R is connected to any substitutable position of the benzene ring, and the functional group of R is not limited to one. For example,

Refers to a benzene ring containing 1 to 6 R functional groups. Suitable examples include, but are not limited to:

In the present application, "cycloalkyl" refers to a non-aromatic hydrocarbon containing ring carbon atoms, which can be a monocyclic alkyl, a spirocyclic alkyl, or a bridged cycloalkyl. Phrases containing this term, for example, "C ₅ ~ C ₇ cycloalkyl" refers to a cycloalkyl containing 5 to 7 carbon atoms, each occurrence of which can be independently C ₅ cycloalkyl, C ₆ cycloalkyl, C ₇ cycloalkyl. Suitable examples include, but are not limited to, cyclopentyl, cyclohexyl, and cycloheptyl. In addition, "cycloalkyl" may also contain one or more double bonds, and representative examples of cycloalkyl containing double bonds include cyclopentenyl, cyclohexenyl, and cyclohexadienyl.

In the present application, phrases containing "asymmetric branched alkyl", for example, "C ₃ to C ₆ asymmetric branched alkyl" refer to asymmetric branched alkyl containing 3 to 6 carbon atoms, and each occurrence can be independently C ₃ asymmetric branched alkyl, C ₄ asymmetric branched alkyl, C ₅ asymmetric branched alkyl, C ₆ asymmetric branched alkyl. Suitable examples include, but are not limited to, methylethyl, methylpropyl, ethylpropyl, methylbutyl, ethylbutyl or methylpentyl.

The present application provides a resin composition, which comprises the following components in parts by weight:

Wherein, the structural formula of the modified polyphenylene ether resin is:

Wherein, m and n are both positive integers, the sum of m and n is 5 to 50, the number average molecular weight of the modified polyphenylene ether resin is 500 to 4000; and R is a cycloalkyl group or an asymmetric branched alkyl group.

In one example, the cycloalkyl group is a C ₅ -C ₇ cycloalkyl group.

In one example, the asymmetric branched alkyl group is a C ₃ -C ₆ asymmetric branched alkyl group.

Preferably, the number average molecular weight of the modified polyphenylene ether resin is 800 to 3000. Further, the number average molecular weight of the modified polyphenylene ether resin is 1000 to 2500. More preferably, the number average molecular weight of the modified polyphenylene ether resin is 1200 to 2200.

In the present application, the number average molecular weight may be a value measured by a common molecular weight measurement method, and may be, but is not limited to, a value measured by gel permeation chromatography (GPC).

In the present application, by limiting the number average molecular weight, the values of m and n, and the R functional group of the modified polyphenylene ether resin, the modified polyphenylene ether resin has a smaller molecular weight and has the advantages of good distribution and high solvent selectivity; when applied to a resin composition, it has the advantages of good heat resistance, good structural stability, good toughness, high solvent selectivity, and a small polymerization molecular weight and good distribution.

It is understandable that in the present application, the average number of vinyl groups at the molecular end of each molecule of the modified polyphenylene ether compound in the modified polyphenylene ether resin is not particularly limited. Specifically, it is preferably 1 to 5, more preferably 1 to 3, and further preferably 1.5 to 3. If the number of terminal functional groups is too small, it tends to be difficult to obtain sufficient heat resistance of the cured product. In addition, if the number of terminal functional groups is too large, the reactivity becomes too high, and undesirable conditions such as reduced storage stability of the resin composition or reduced fluidity of the resin composition may occur. That is, if the modified polyphenylene ether compound is used, problems with formability may arise due to insufficient fluidity, for example, forming defects such as voids may occur during multi-layer forming, and it is difficult to obtain a wiring board with high reliability.

In one example, the resin composition includes 50 to 150 parts by weight of the modified polyphenylene ether resin. Specifically, the weight of the modified polyphenylene ether resin includes but is not limited to 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, 120 parts, 140 parts or 150 parts.

In one example, the resin composition includes 10 to 100 parts of hydrocarbon resin by weight. Specifically, the weight of the hydrocarbon resin includes but is not limited to 10, 20, 50, 70, 80, 90 or 100 parts. Further, the resin composition includes 20 to 100 parts of hydrocarbon resin by weight.

In one example, the resin composition includes 10 to 100 parts of bismaleimide resin by weight. Specifically, the weight of the bismaleimide resin includes but is not limited to 10 parts, 20 parts, 40 parts, 50 parts, 60 parts, 80 parts or 100 parts. Further, the resin composition includes 20 to 80 parts of bismaleimide resin by weight.

In one example, the resin composition includes 100 to 400 parts of inorganic filler by weight. Specifically, the weight of the inorganic filler includes but is not limited to 100 parts, 200 parts, 300 parts or 400 parts.

In one example, the resin composition includes 5 to 100 parts of a flame retardant by weight. Specifically, the weight of the flame retardant includes but is not limited to 5, 6, 7, 10, 20, 30, 40, 50, 60, 70, 80, 90 or 100 parts.

In one example, the resin composition includes 20 to 80 parts of a crosslinking agent by weight. Specifically, the weight of the crosslinking agent includes but is not limited to 20 parts, 30 parts, 35 parts, 38 parts, 39 parts, 40 parts, 42 parts, 45 parts, 50 parts, 60 parts, 70 parts, 79 parts or 80 parts.

In one example, the resin composition includes 0.05 to 5 parts of an initiator by weight. Specifically, the weight of the initiator includes but is not limited to 0.05, 0.09, 0.1, 0.11, 0.15, 0.2, 1, 2, 3, 4 or 5 parts.

In one example, the ratio of the modified polyphenylene ether resin to the hydrocarbon resin is 100 parts: (20-60) parts.

By adjusting the mass fractions of the modified polyphenylene ether resin and the hydrocarbon resin, the dielectric properties of the resin composition can be fully improved, the viscosity of the resin composition can be effectively controlled, and the permeability of the resin composition into the substrate can be improved.

In one example, the following components are included in parts by weight:

In one example, the cycloalkyl group is selected from any one of cyclopentyl, cyclohexyl, cycloheptyl, 3-methylcyclohexyl, 3-methylcycloheptyl or 3,5-dimethylcyclohexyl.

In one example, the asymmetric branched alkyl group is selected from any one of methylethyl, methylpropyl, ethylpropyl, methylbutyl or ethylbutyl.

In one example, the hydrocarbon resin includes one or both of polybutadiene and a copolymer of butadiene and styrene.

其中，m表示丁二烯的摩尔数，n表示苯乙烯的摩尔数。It can be understood that the structural formula of the copolymer of butadiene and styrene is

Here, m represents the number of moles of butadiene, and n represents the number of moles of styrene.

The number average molecular weight of the copolymer of polybutadiene and styrene plays an important role in improving the glass transition temperature and heat resistance of the resin composition. If the molecular weight of the hydrocarbon resin is too small, the glass transition temperature or the heat resistance of the cured product tends to decrease. If the molecular weight of the hydrocarbon resin is too large, the viscosity of the resin composition or the viscosity during heating and forming will be larger. Therefore, if the weight average molecular weight of the hydrocarbon resin is within the above range, the glass transition temperature and heat resistance are more excellent, and the thermal degradation of the dielectric properties can be further suppressed.

In one example, the hydrocarbon resin is a copolymer of butadiene and styrene.

Furthermore, the number average molecular weight of the copolymer of butadiene and styrene is 1000-20000, the molar content of butadiene in the copolymer of butadiene and styrene is 40%-90%, and the molar content of styrene in the copolymer of butadiene and styrene is 10%-60%.

In one example, the bismaleimide resin includes one or more of biphenyl bismaleimide resin, polyphenylmethane maleimide and bis(3-ethyl-5-methyl-4-maleimidophenyl)methane.

Preferably, the structural formula of the bismaleimide resin is:

其中，n为正整数。

Wherein, n is a positive integer.

In one example, the cross-linking agent includes one or more of an allyl compound, styrene, divinylbenzene, an acrylate compound, a methacrylate compound, polybutadiene, and a bismaleimide compound.

、

中的一种或多种，其中，n1、n2均为正整数。In one example, the flame retardant includes

,

One or more of , wherein n1 and n2 are both positive integers.

The halogen-free flame retardant selected in the present application can effectively reduce the dielectric properties without affecting the glass transition temperature.

In one example, the initiator includes one or more of α,α′-bis(tert-butylperoxym-isopropyl)benzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, benzoyl peroxide, 3,3′,5,5′-tetramethyl-1,4-diphenolquinone, tetrachlorobenzoquinone, 2,4,6-tri-tert-butylphenoxy, tert-butylperoxyisopropyl monocarbonate and azobisisobutyronitrile.

In one example, the inorganic filler includes one or more of silica, alumina, titanium oxide, mica, aluminum hydroxide, magnesium hydroxide, talc, aluminum borate, barium sulfate, and calcium carbonate.

Preferably, the inorganic filler includes one or more of silica, mica and talc.

More preferably, the inorganic filler is spherical silica.

。In one example, the flame retardant is

.

In one example, the resin composition further includes a solvent.

The solvent can change the solid content of the resin composition and adjust the viscosity of the resin composition.

In one example, the solvent includes one or more of methanol, ethanol, ethylene glycol monomethyl ether, acetone, butanone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide, dimethylacetamide and propylene glycol methyl ether.

In one example, the resin composition further includes a functional resin.

In one example, the functional resin includes one or more of epoxy resin, phenolic resin, acid anhydride, benzoxazine resin, rubber and modified PTFE.

The present application provides a prepreg, which comprises a substrate and the resin composition described in any one of the above examples supported on the substrate.

The present application also provides a method for preparing a prepreg, the preparation method comprising the following steps:

Mixing the components of the resin composition in a solvent to prepare the resin composition;

The resin composition is loaded on a substrate to prepare a prepreg.

It is understandable that the present application does not limit the method of mixing the components in the solvent, as long as the method can be used to mix the components. For example, the components that can be dissolved in the organic solvent can be first put into the organic solvent to completely dissolve, and heating can be performed as needed; then the components that are insoluble in the organic solvent, such as flame retardants and inorganic fillers, are added and stirred and mixed using a ball mill, a bead mill, a planetary mixer, a roller mill, etc.

The present application does not limit the manner in which the resin composition is loaded on a substrate. Examples include impregnation, coating, and spraying. In addition, as a method for manufacturing a prepreg, the resin composition is loaded on a substrate and then dried and heated. In addition, the impregnation, coating, and spraying steps in the present application may also be repeated multiple times as needed. In addition, multiple thermosetting resin compositions with different compositions and solid contents may be used for repeated impregnation to adjust to the final composition and glue content.

The present application also provides a prepreg, which comprises a substrate and the resin composition described in any one of the above embodiments loaded on the substrate.

In the present application, the substrate is a well-known inorganic or organic fiber material, and the inorganic fiber substrate includes but is not limited to glass fiber cloth, carbon fiber, silicon carbide fiber or asbestos fiber. The organic fiber substrate includes but is not limited to nylon, ultra-high molecular weight polyethylene fiber, aramid fiber, polyimide fiber, polyester fiber or cotton fiber. The glass fiber cloth includes but is not limited to E, NE, D, S, T types.

Preferably, the substrate is glass fiber cloth.

More preferably, the substrate is a flattened glass fiber cloth. The flattening process is a process of continuously pressing the glass cloth with a pressing roller at an appropriate pressure to compress the yarn into a flat state.

The present application also provides a method for preparing a prepreg, comprising the following steps:

The prepreg is heated to prepare the prepreg.

In one example, the heating process parameters include: the temperature is set to 80° C. to 200° C., and the time is set to 1 min to 20 min.

Furthermore, the heating process parameters include: the temperature is set to 110° C. to 190° C., and the time is set to 2 min to 10 min.

The present application also provides an application of the prepreg in any of the above examples in the preparation of a laminate, a copper-clad laminate or a wiring board.

The present application also provides a laminate, which includes the prepreg described in the above embodiment.

The present application also provides a method for preparing a laminate, comprising the following steps:

One or more prepregs are selected and laminated to prepare the laminate.

In one example, the lamination process parameters include: temperature set at 170° C. to 250° C., pressure set at 10 kgf/cm ² to 30 kgf/cm ² , vacuum degree < 2 kPa, and hot pressing for 60 min to 120 min.

The present application also provides a copper clad laminate, which includes the prepreg described in the above embodiment and a metal foil covering one side or both sides of the laminated prepreg.

In one example, the thickness of the metal foil is 3 μm to 70 μm.

In order to make the purpose and advantages of the present invention clearer, the resin composition, prepreg and its application of the present invention are further described in detail below in conjunction with specific examples. It should be understood that the specific examples described herein are only used to explain the present invention and shall not be used to limit the present invention. The following examples do not include other components except inevitable impurities unless otherwise specified. The drugs and instruments used in the examples are conventionally selected in the art unless otherwise specified. The experimental methods for which specific conditions are not specified in the examples are implemented according to conventional conditions, such as the conditions described in the literature, books or the methods recommended by the manufacturer.

The raw materials used in the following examples and comparative examples are as follows:

[Modified polyphenylene ether resin]

SA9000, methacrylic acid modified polyphenylene ether resin, manufactured by Sabic;

OPE-1200-2st, styrene-modified polyphenylene ether resin, manufactured by Mitsubishi Corporation;

[Crosslinking agent]

TAIC, triallyl isocyanurate, manufactured by Nippon Chemical Industry Co., Ltd.;

[Hydrocarbon resin]

R100, butadiene-styrene copolymer, manufactured by Cray Valley Company;

B-1000, polybutadiene, manufactured by Caoda Company;

[Bismaleimide resin]

MIR-3000, biphenyl-type bismaleimide resin, manufactured by Nippon Kayaku Co., Ltd.;

BMI-2300, polyphenylmethane maleimide, manufactured by Yamato Chemical Co., Ltd., Japan;

BMI-5100, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, manufactured by Yamato Chemical Co., Ltd., Japan;

[Flame retardant]

GU304, double DPO type phosphorus-containing flame retardant, melting point 320℃, P%=12%, molecular formula

科宜公司制造；

Manufactured by Keyi Corporation;

PX-200, resorcinol dixylyl phosphate, P% = 9%, manufactured by Daba Company;

SPB-100, phosphazene compound, P% = 13%, manufactured by Otsuka Corporation;

[Inorganic filler]

SC2300-SVJ, double bond treated spherical silica, manufactured by Admatechs;

[Initiator]

PERBUTYL P, 1,3-bis(butylperoxyisopropyl)benzene, manufactured by NOF Corporation of Japan;

[Fiberglass cloth]

Fiberglass cloth, 2116 cloth, manufactured by Honghe Company.

The compositions of the resin compositions provided in the embodiments and comparative examples are as follows:

The preparation process of the resin composition of the embodiment and the comparative example is as follows:

The modified polyphenylene ether resin is mixed with toluene, and the mixture is heated to 60°C and fully stirred to fully dissolve the modified polyphenylene ether resin in toluene to obtain a toluene solution with a solid content of 50% by mass. Then, a crosslinking agent, a hydrocarbon resin, and a bismaleimide resin are added thereto to reach the proportions in each embodiment and comparative example in the table, and stirred for 2 hours to fully dissolve them. Finally, a flame retardant, an inorganic filler, an initiator and an appropriate amount of toluene are further added, and the mixture is fully dispersed using a bead mill to prepare a resin composition.

The preparation process of the prepregs of the embodiments and comparative examples is as follows:

The glass fiber cloth was immersed in the resin composition prepared in the embodiment and the comparative example, the temperature was set to 160°C, and heated for 5 minutes to prepare a prepreg. At this time, the solid content of the resin composition can be adjusted to obtain a prepreg with a mass ratio of 50%.

The preparation process of the copper clad laminate of the embodiment and the comparative example is as follows:

Eight prepregs were stacked respectively, and 35 μm HVLP2 copper foil was placed on both sides. The prepregs were heated and pressed at a temperature of 210° C. and a pressure of 3 MPa for 2 hours to prepare a copper clad laminate with a thickness of about 0.8 mm.

Performance Tests of Copper Clad Laminates of Examples and Comparative Examples

1. Peel strength: Tested using a universal tensile testing machine in accordance with IPC-TM-650 2.4.8.

2. Glass transition temperature (Tg): The glass transition temperature (Tg) is measured using a dynamic mechanical analyzer (DMA) (DMA850 manufactured by TA Instruments) at a heating rate of 3°C/min. The test specification for glass transition temperature uses the Institute for Interconnecting and Packaging Electronic Circuits (IPC) IPC-TM-650 2.4.25C and 24C test methods.

3. Dielectric constant and dielectric loss measurement: Agilent E5071C network analyzer was used to measure the dielectric constant (Dk) and dielectric loss (Df) at an operating frequency of 10 MHz according to IPC-TM-650 2.5.5.13.

4. 288℃ solder resistance heat resistance test: Immerse the test piece that has been steamed in a PCT pressure cooker for 2 hours in a 288℃ solder furnace for 6 minutes, and record whether the test piece explodes.

5. Test of thermal expansion coefficient and expansion rate in X/Y/Z axis direction: Measured by TA instrument company's TA Q800 thermal expansion analyzer, with the measuring temperature of 50℃～260℃ and the heating rate of 10℃/min, test the thermal expansion coefficient and expansion rate of the sample in X/Y/Z axis direction.

6. Flame retardant test: Refer to UL-94 specification, use Bunsen burner, methane gas and ammeter to test the time it takes for the sample to automatically extinguish after burning, and determine the grade based on this time.

7. Elastic modulus: According to GB/T 22315-2008, the elastic modulus is tested using a universal tensile testing machine.

The test results of the copper clad laminates of the above embodiments and comparative examples are as follows:

From the performance of the copper-clad laminate provided by the above-mentioned embodiments and comparative examples, it can be seen that: by comparing Embodiment 1 with Comparative Example 1, the copper-clad laminate prepared by using styrene-modified polyphenylene ether resin as the modified polyphenylene ether resin can enhance the peel strength of the copper-clad laminate while ensuring a lower dielectric constant and dielectric loss. By comparing Embodiment 4 with Comparative Example 2, it is found that the performance of the copper-clad laminate prepared by combining styrene-modified polyphenylene ether resin with butadiene and styrene copolymer is better than that of methacrylic acid-modified polyphenylene ether resin and polybutadiene, and the copper-clad laminate in Embodiment 4 can have a lower expansion coefficient while ensuring a lower dielectric constant and dielectric loss; by comparing Embodiment 1 with Comparative Example 3, it can be found that if the proportion of inorganic filler added to the resin composition is too low, the elastic modulus will be insufficient, the X/Y axis expansion coefficient will be too high, and the dielectric loss will be too large.

The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

The above-described embodiments only express several implementation methods of the present application, which is convenient for understanding the technical solution of the present application in detail, but it cannot be understood as limiting the scope of protection of the invention patent. It should be pointed out that for ordinary technicians in this field, without departing from the concept of the present application, several modifications and improvements can be made, which all belong to the scope of protection of the present application. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided in the present application are all within the scope of protection of the claims attached to the present application. Therefore, the scope of protection of the patent of this application shall be based on the content of the attached claims, and the description can be used to interpret the content of the claims.

Claims (11)

1. The resin composition is characterized by comprising the following components in parts by weight:

wherein the structural formula of the modified polyphenyl ether resin is as follows:

wherein m and n are positive integers, the sum of m and n is 5-50, and the number average molecular weight of the modified polyphenyl ether resin is 500-4000; r is cycloalkyl or asymmetric branched alkyl.

2. The resin composition according to claim 1, wherein the cycloalkyl group is C ₅ ～C ₇ Cycloalkyl;

the asymmetric branched alkyl group is C ₃ ～C ₆ An asymmetric branched alkyl group.

3. The resin composition according to claim 1, wherein the ratio of the modified polyphenylene ether resin to the hydrocarbon resin is 100 parts by weight to (20 to 60 parts by weight).

4. The resin composition according to claim 1, which comprises the following components in parts by weight:

5. the resin composition according to any one of claims 1 to 4, wherein the cycloalkyl group is selected from any one of cyclopentyl, cyclohexyl, cycloheptyl, 3-methylcyclohexyl, 3-methylcycloheptyl, and 3, 5-dimethylcyclohexyl;

the asymmetric branched alkyl is selected from any one of methylethyl, methylpropyl, ethylpropyl, methylbutyl or ethylbutyl.

6. The resin composition according to any one of claims 1 to 4, wherein the hydrocarbon resin comprises one or two of polybutadiene, a copolymer of butadiene and styrene.

7. The resin composition of claim 6 wherein the hydrocarbon resin is a copolymer of butadiene and styrene;

further, the number average molecular weight of the copolymer of butadiene and styrene is 1000-20000, the molar content of butadiene in the copolymer of butadiene and styrene is 40-90%, and the molar content of styrene in the copolymer of butadiene and styrene is 10-60%.

8. The resin composition according to any one of claims 1 to 4, wherein the resin composition has one or more of the following features:

(1) The bismaleimide resin comprises one or more of biphenyl bismaleimide resin, polyphenylmethane maleimide and bis (3-ethyl-5-methyl-4-maleimidophenyl) methane;

(2) The crosslinking agent comprises one or more of allyl compounds, styrene, divinylbenzene, acrylate compounds, methacrylate compounds, polybutadiene, and bismaleimide compounds;

(3) The flame retardant comprises

Wherein n1 and n2 are positive integers;

(4) The initiator comprises one or more of alpha, alpha ' -bis (tertiary butyl peroxyisopropyl) benzene, dicumyl peroxide, 2, 5-dimethyl-2, 5-di (tertiary butyl peroxy) hexane, di-tertiary butyl peroxide, 2, 5-dimethyl-2, 5-di (tertiary butyl peroxy) -3-hexyne, benzoyl peroxide, 3', 5' -tetramethyl-1, 4-diphenoquinone, tetrachlorobenzoquinone, 2,4, 6-tri-tertiary butyl phenoxy, tertiary butyl peroxyisopropyl monocarbonate and azobisisobutyronitrile;

(5) The inorganic filler includes one or more of silica, alumina, titanium oxide, mica, aluminum hydroxide, magnesium hydroxide, talc, aluminum borate, barium sulfate, and calcium carbonate.

9. The resin composition according to claim 8, wherein the flame retardant is

。

10. A prepreg comprising a substrate and the resin composition of any one of claims 1 to 9 supported on the substrate.

11. Use of the prepreg according to claim 10 for the preparation of a laminate, a copper-clad plate or a wiring board.